CN102027055B - Rubber composition for tyre including a novel anti-oxidant system - Google Patents
Rubber composition for tyre including a novel anti-oxidant system Download PDFInfo
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- CN102027055B CN102027055B CN2009801168242A CN200980116824A CN102027055B CN 102027055 B CN102027055 B CN 102027055B CN 2009801168242 A CN2009801168242 A CN 2009801168242A CN 200980116824 A CN200980116824 A CN 200980116824A CN 102027055 B CN102027055 B CN 102027055B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
- Y10T152/10765—Characterized by belt or breaker structure
- Y10T152/1081—Breaker or belt characterized by the chemical composition or physical properties of elastomer or the like
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Abstract
The invention relates to a rubber composition particularly intended for a tyre and including at least one diene elastomer, a reinforcing filler, a cross-linking system and an anti-oxidant system, characterised in that said anti-oxidant system includes at least two anti-oxidants A and B, A being an N-alkyl-N'-phenyl-paraphenylenediamine of the formula (I) and B being a 4,4',4'-tris(alkylamino)-triphenylamine of the formula (II), wherein R1, R2, R3, R4 are identical or different and each are a linear or branched alkyl group including 1 to 12 carbon atoms or a cycloalkyl group including 5 to 8 carbon atoms, the A/B weight ratio ranging from 0.1 to 5.0. Said anti-oxidant system imparts to the composition of the invention a better long-term resistance to fatigue and crack propagation.
Description
Technical field
The present invention relates to the diene elastomer composition, also relate to the antioxidant for the anti-aging protection of this composition.
More particularly, the present invention relates to be used to form the diene elastomer composition of all or part of rubber matrix of tire, particularly the crown reinforcement of these tires is also referred to as " band bundle ".
Background technology
Brief review has the tire of radial carcass reinforcement, it comprises tyre surface, two not extensible tyre beads in known manner, tyre bead is connected to two sidewalls of tyre surface and circumferential (circumferentially) band bundle of placing between carcass reinforcement and tyre surface, this band bundle is comprised of various rubber curtain layer of cloths (plies) (or " layer (layers) "), described rubber layer can by or can't help metal or textile type and strengthen element (or " reinforcement "), strengthen such as cord or monofilament.
Tire belt is comprised of at least two overlapping belts or band bundle cord body (sometimes being called " work " cord body or " intersection " cord body) usually, in practice, the configuration parallel to each other in one deck of the reinforcement of described belt or band bundle cord body, but intersect to another layer from one deck, that is to say that described reinforcement tends to, no matter whether symmetry, favours the center circle side face with the common angle between 10 ° and 45 °, and described angle depends on the tyre type of discussing.Each of these two cross-levels is comprised of common rubber matrix based on isoprene (" the calendering glue " that sometimes is called the coating reinforcement).Cross-level can be by the various width that have with the situation variation; and other auxiliary rubber cord bodies or the rubber layer that can contain or not contain reinforcement carry out finishing; can mention for example simple rubber pad, act as the layer that is called " protection " layer that all the other band bundles of protection avoid external attack, perforation, perhaps comprise basically orientation (layer that is called " zero degree " layer) along the circumferential direction no matter and than cross-level be radially outer or inside reinforcement be called " stirrup " layer (" hoop reinforcement " layer) layer.
This tire belt must satisfy many in known manner, is the requirement of contradiction sometimes, particularly:
(i) rigidity as far as possible under low distortion is because it helps the reinforcement tyre crown considerably;
(ii) have interior region overheated of alap hysteresis crown when rolling to be minimized on the one hand, reduce on the other hand the rolling resistance (itself and fuel economy synonym) of tire; And
(iii) last, have high weather resistance, particularly for the separation or cracking phenomena (being known as the problem of term " division ") of the cross-level end in " shoulder " zone of tire.
The rubber combination that the third condition especially requires to add the tire belt formation has high resistance of crack propagation and resistance to thermooxidation, the resistance to thermooxidation that particularly provides the antioxidant of effective anti-aging protection to obtain by use.
This requirement is high especially for the cover tire of heavy vehicle, and the cover tire of heavy vehicle is designed to, and when its tyre surface that comprises reaches critical wear and spends after long-time the rolling, it can be renovated one or many.
In rubber composition for tire; especially intrafascicular being with of this tire; the long-term derivative family that belongs to Ursol D (PPD) as anti-aging protectant antioxidant; for example be good antioxidant and the N-sec.-propyl-N ' of antiozonidate-phenyl-Ursol D (I-PPD) or N-1 simultaneously; 3-dimethylbutyl-N '-phenyl-Ursol D (6-PPD) (referring to for example applying for WO2004/033548, WO 2005/063510, WO 2005/133666).
Now, the applicant finds in research process, antioxidant with another the specific antioxidant that also is not used for so far tire replaces a part of this Ursol D to derive might increase Long-term Anti fatigability and resistance of crack propagation for these rubber combinations of tire.
Summary of the invention
Therefore, first purpose of the present invention relates to a kind of rubber combination based at least a diene elastomer, reinforcing filler, cross-linking system and antioxidant series, it is characterized in that described antioxidant series comprises at least two kinds of antioxidants " A " and " B ":
A. corresponding to the N-alkyl-N '-phenyl-p-phenylenediamine of formula (I):
B. corresponding to formula (II) 4,4 ', 4 "-three (alkylamino) triphenylamine:
Wherein, R
1, R
2, R
3And R
4Identical or different, each expression has the linearity of 1 to 12 carbon atom or the alkyl of branching, perhaps has the cycloalkyl of 5 to 8 carbon atoms, and the A/B weight ratio is between 0.1 and 5.0.
Therefore the invention provides tire belt, and these tires itself, a kind of whole machine balancing of novel and particularly advantageous performance.
Of the present invention another themes as composition of the present invention for the manufacture of new tire or for the purposes of renovating old tire, the most particularly in the situation of heavy vehicle tyre.
Rubber combination of the present invention makes by the method that consists of another theme of the present invention, and described method comprises the steps:
Mediate whole mixture until reach maximum temperature between 110 ℃ and 190 ℃ by heat engine tool in one or more stages, add in the diene elastomer in the mixing tank:
-reinforcing filler; With
-antioxidant series;
Whole mixture is cooled to temperature below 100 ℃;
Then add cross-linking system;
Mediate whole mixture until the maximum temperature below 110 ℃,
Described method is characterised in that described antioxidant series comprises at least two kinds of aforementioned antioxidants " A " and " B ", and the A/B weight ratio is between 0.1 and 5.0.
The present invention also relates to comprise any tire of composition of the present invention, particularly no matter this tire is meridian line style or non-meridian line style.
Tire of the present invention is intended to assemble the Motor vehicles such as Types Below especially: passenger vehicle, SUV (sport vehicle), sulky vehicle (especially motorcycle), aircraft, for example be selected from the industrial vehicle of van or " heavy type " vehicle, described " heavy type " vehicle is subway, bus, heavy-duty highway carrier vehicle (truck, tractor, trailer), such as the Der Gelaendewagen of agricultural machine or civil engineering machine, and other carrier vehicles or trolley.
The present invention itself also relates to the antioxidant series of the anti-aging protection that can be used in particular for rubber composition for tire, it is characterized in that described system comprises at least two kinds of aforementioned antioxidants " A " and " B ", and the A/B weight ratio is between 0.1 and 5.0.
According to following description and particular exemplary embodiments, and the expression relevant with these embodiment have the synoptic diagram (single accompanying drawing) of radial section of the heavy vehicle tyre of radial carcass reinforcement, will easily understand the present invention and advantage thereof.
Embodiment
I.
Used measurement and test
Solidifying front and back according to sign rubber combination as described below.
A) rheological measurement:
This measurement uses concussion chamber rheometer to carry out under 150 ℃ according to standard DIN 53529-the 3rd part (June nineteen eighty-three).The variation of composition with the sclerosis of vulcanization reaction described in the rheology torque over time.Measurement is carried out according to standard DIN 53529-part 2 (March nineteen eighty-three): t
iBe induction time, namely vulcanization reaction begins the required time; t
α(t for example
99) for obtaining the conversion of α %, i.e. required time of the α % of minimum torque and torque capacity difference (for example 99%).Also measured by K and represented (to divide
-1Meter) single order transformation efficiency constant, it is obtained by the conversion calculations between 30% and 80%, and this is so that might assess sulfuration kinetics.
B) tension test:
These tests might be determined elastic stress and fracture property.Unless otherwise indicated, the normes Francaises NF T 46-002 in these experimental evidences in September, 1988 carries out.In for the second time elongation (namely after debugging cycle), measure in 10% elongation (being expressed as respectively MA10 and E10), 100% elongation (being respectively MA100 and E100) and 300% and extend " nominal " secant modulus under (being respectively MA300 and E300) (or apparent stress, in MPa) or "True" the secant modulus actual cross-section of test specimen (in this case with respect to).All these stretch to measure and carry out according to normes Francaises NF T 40-101 (in December, 1979) under conventional temperature (23 ± 2 ℃) and humidity (50 ± 5% relative humidity) condition.Also under 23 ℃ temperature, measure tensile strength (in MPa) and extension at break (in %).
C) " MFTRA " test:
According to normes Francaises NF T 46-021, use Monsanto (" MFTR " type) machine, comprising 1 millimeter and standing low frequency until on the test specimen of the repeat pull of 20% elongation in known manner, meter is shown fatigue resistance and the anti-otch extendability (formerly causing lower) of cycle number or relative unit (u.r.), until the test specimen fracture.
On the one hand under initial state, after 24 days accelerate thermal-oxidative ageing, carry out above-mentioned experiment on the other hand, the composition sample that then will test places the ventilated drying oven under the ambient moisture of the temperature that remains on 77 ℃ and 40%.The improved result of value representation who is higher than control value (be 100 with its Set arbitrarily), i.e. higher patience.
II.
Detailed description of the present invention
Elastic composition of the present invention is based on following at least composition: (i) a kind of (at least a) diene elastomer; (ii) a kind of (at least a) reinforcing filler; (iii) cross-linking system; (iv) antioxidant series as described below.
Certainly, statement " based on ... composition " be interpreted as meaning to comprise the reaction product of used various compositions and/or the composition of mixture, in these basal component some can, or be intended in the various manufacturing stage processes of rubber combination, band bundle and tire particularly at least in part together reaction in their sulfidation.
In this manual, unless explicitly point out in addition, all percentage ratio (%) of expression is % by weight.
II-1. diene elastomer
Term " diene " elastomerics (or rubber, think both synonyms) is interpreted as usually meaning the elastomerics that at least part of (being homopolymer or multipolymer) is derived from diene monomers (monomer that namely has two (conjugation or non-conjugated) carbon-to-carbon double bonds).
Diene elastomer can be divided into two classes in known manner: those of those of " basically unsaturated " and " basically saturated ".Usually, statement " basically undersaturated diene elastomer " is interpreted as at this paper and means at least part of diene elastomer that derives from conjugate diene monomer, its have 15% (% by mole) above diene units number or diene source (conjugated diolefine) unit number.Therefore, for example, do not fall into above-mentioned definition such as the diene elastomer of isoprene-isobutylene rubber or EPDM type diene/alpha-olefin copolymer, it is called especially " basically saturated diene elastomer " (little or minimum diene source unit number, common below 15%).In the diene elastomer class of " basically unsaturated ", statement " highly undersaturated diene elastomer " is interpreted as that especially meaning diene source (conjugated diolefine) unit number is diene elastomer more than 50%.
Provide these definition, should more particularly understand the diene elastomer that can be used in the composition of the present invention and mean:
(a)-preferably have any homopolymer that the conjugate diene monomer of 4 to 12 carbon atoms obtains by polymerization;
(b)-and by making the each other copolymerization of one or more conjugated diolefines, any multipolymer that the vinyl aromatic compounds copolymerization that perhaps makes one or more conjugated diolefines and one or more preferably have 8 to 20 carbon atoms obtains;
(c)-by making ethene, preferably having a terpolymer that the alpha-olefin of 3 to 6 carbon atoms and the non-conjugated diene monomers copolymerization that preferably has 6 to 12 carbon atoms obtain, the elastomerics that is for example obtained by the non-conjugated diene monomers (especially such as Isosorbide-5-Nitrae-hexadiene, ethylidene norbornene and Dicyclopentadiene (DCPD)) of ethene, propylene and aforementioned type; With
(d)-multipolymer of iso-butylene and isoprene (isoprene-isobutylene rubber), and this analog copolymer of halo, particularly chloro or bromo type.
Although the present invention is applicable to the diene elastomer of any type, the tire those skilled in the art should be appreciated that the present invention at first uses basically undersaturated diene elastomer, particularly above-mentioned (a) or (b) class.
More preferably, diene elastomer is selected from polyhutadiene (BR), natural rubber (NR), synthetic polyisoprenes (IR), various butadienecopolymer, various isoprene copolymer or these elastomeric adulterants.This multipolymer more preferably is selected from butadiene-styrene (SBR) multipolymer (no matter the latter makes by the polymerization in the emulsion (ESBR) or by the polymerization in the solution (SSBR)), isoprene-butadiene (BIR) multipolymer, isoprene-vinylbenzene (SIR) multipolymer or isoprene-butadiene-vinylbenzene (SBIR) multipolymer.In polyhutadiene, suitable be in particular 1,2 unit content (% by mole) between 4% and 80% those, perhaps suitable-Isosorbide-5-Nitrae unit content (% by mole) be more than 80% those.In synthetic polyisoprenes, specially suitable is suitable-Isosorbide-5-Nitrae-polyisoprene, preferably suitable-Isosorbide-5-Nitrae linkage content (% by mole) be more than 90% those.In divinyl or isoprene copolymer, these are interpreted as meaning especially by making at least a multipolymer that obtains with one or more vinyl aromatic compounds copolymerization with 8 to 20 carbon atoms in these two kinds of monomers.Suitable vinyl aromatic compounds is for example vinylbenzene, ortho-, meta-or p-, meta-and p-methylstyrene, commercially available " Vinyl toluene " mixture, p-t-butyl styrene, methoxy styrene, chloro-styrene, vinyl Three methyl Benzene (vinylmesitylene), Vinylstyrene and vinylnaphthalene.Described multipolymer can contain in the diene units between 99% and 20% and the vinyl aromatic units between 1% and 80%.
Elastomerics can have and depends on used polymerizing condition, particularly depends on the existence of properties-correcting agent and/or random reagent (randomizing agent) or does not exist and any microstructure of the consumption of used properties-correcting agent and/or random reagent.Elastomerics can for example be block, random, sequence or little sequence elastomerics, and can make in dispersion or in solution, and they can be coupling and/or star-branched, or functionalized with coupling agent and/or star-branched reagent or functionalized reagent.Be coupled to functional group that mentioning of carbon black for example comprise the C-Sn key or the functional group of amination, such as benzophenone; Be coupled to and strengthen mentioning silanol functional for example or having the polysiloxane functional group (for example being described among FR 2 740 778 or the US 6 013 718) of silanol end of mineral filler (such as silicon-dioxide), alkoxysilane groups (for example being described among FR 2 765 882 or the US 5 977 238), carboxyl (for example is described in WO 01/92402 or US 6 815 473, among WO 2004/096865 or the US 2006/0089445) or polyether group (for example being described among EP 1 127 909 or the US 6 503 973).Can mention that also the elastomerics (such as SBR, BR, NR or IR) of epoxidation type is as other examples of functionalized elastomeric body.
Composition of the present invention preferably is intended to for tire, the carcass reinforcement of the tire of industrial vehicle (such as van, heavy vehicle) particularly, and be intended to crown reinforcement for the tire of passenger vehicle and industrial vehicle.
At least a isoprene elastomerics of preferred use, be isoprene homopolymer or multipolymer, in other words, be selected from the diene elastomer of natural rubber (NR), synthetic polyisoprenes (IR), various isoprene copolymer or these elastomeric adulterants.In isoprene copolymer, mention especially iso-butylene/isoprene (isoprene-isobutylene rubber-IIR), isoprene/vinylbenzene (SIR), isoprene/butadiene (BIR) or isoprene/butadiene/vinylbenzene (SBIR) multipolymer.
The isoprene elastomerics is preferably natural rubber or synthetic suitable-Isosorbide-5-Nitrae polyisoprene.In these synthetic polyisoprenes, preferably use suitable-Isosorbide-5-Nitrae linkage content (% by mole) be more than 90%, the more preferably polyisoprene more than 98%.
By with above-mentioned isoprene elastomerics fusion (namely mixing), the diene elastomer except the isoprene elastomerics that composition of the present invention can contain preferred a small amount of (being that 50phr is following).The isoprene elastomerics is 75 to 100 % by weight of all diene elastomers more preferably, i.e. 75 to 100phr (phr=weight part/100 part rubber).
As this diene elastomer except the isoprene elastomerics, especially mention and be selected from especially following any unsaturated type diene elastomer: polyhutadiene (BR), particularly suitable-1,4 or 1,2-syndiotactic polybutadiene and 1,2-unit content (% by mole) between 4% and 80% those; Butadienecopolymer, especially phenylethylene/butadiene (SBR) multipolymer and particularly styrene content is between 5 and 50 % by weight, be more in particular between 20 % by weight and 40 % by weight, divinyl part 1, the 2-linkage content (% by mole) between 4% and 65%, instead-the Isosorbide-5-Nitrae linkage content (% by mole) between 30% and 80% those; The adulterant of phenylethylene/butadiene/isoprene (SBIR) multipolymer or these various elastomericss (BR, SBR and SBIR).
For example, when composition was intended to tire for the passenger vehicle type, if use this adulterant, then the mixture of SBR and BR was preferably used as the adulterant with natural rubber, and the mixture of SBR and BR is preferably 25 % by weight following (or 25phr is following).
Composition of the present invention can be used in particular for heavy vehicle tyre band bundle, no matter is new tire or old tire (in the situation of renovation).In this case, the isoprene elastomerics is preferred to be used separately, namely not with another diene elastomer or polymkeric substance fusion.More preferably, this isoprene elastomerics only is natural rubber.
II-2. reinforcing filler
Might use the known reinforcing filler that can strengthen any type of the rubber combination that can be used for making tire, for example organic filler is such as carbon black, or inorganic reinforcing filler, such as silicon-dioxide (must in conjunction with coupling agent).
All carbon blacks are suitable carbon black, especially conventional HAF, ISAF, the SAF type carbon black (being called tire level carbon black) that is used for tire.In the latter, more particularly mention the enhancing carbon black of 100,200 or 300 series (ASTM level), for example N115, N134, N234, N326, N330, N339, N347, N375 carbon black, perhaps depend on intended application, the carbon black of higher series (for example N660, N683, N772, N900).Can be for example with the form of masterbatch (masterbatch) carbon black be added isoprene elastomerics (referring to for example applying for WO 97/36724 or WO 99/16600).
As the example of the organic filler except carbon black, can mention the functionalized polyvinyl aromatics organic filler of describing as among application WO-A-2006/069792 and the WO-A-2006/069793.
In this application, statement " inorganic reinforcing filler " is interpreted as meaning any inorganic or mineral filler (no matter its color or its source (natural or synthetic)) according to definition, its with respect to carbon black be called " in vain " filler, " only " filler (" clear " filler) or even " non-black filler ", itself can strengthen the rubber combination that is intended to for the manufacture of tire, and need not any mode except middle coupling agent, in other words, with regard to enhancement, it can replace conventional tire level carbon black; This filler usually is characterised in that in known manner on its surface and exists hydroxyl (OH).
It is unessential that the enhancing mineral filler with which kind of physical condition provides, and no matter it is form or any other suitable fine and close form of powder, microballon, particle, bead (bead).Certainly, term strengthens mineral filler and also is interpreted as the mixture that means the siliceous and/or aluminium matter filler of the different mixtures, particularly height dispersibility as described below that strengthen mineral fillers.
Suitable inorganic reinforcing filler especially is the mineral filler of siliceous type, particularly silicon-dioxide (SiO
2), the perhaps mineral filler of aluminium matter type, particularly aluminum oxide (Al
2O
3).Used silicon-dioxide can be and well known to a person skilled in the art any enhancing silicon-dioxide, especially BET surface-area and CTAB specific surface area are below 450 meters squared per gram, are preferably any precipitated silica or the pyrogenic silica of 30 to 400 meters squared per gram.As height dispersibility (being called " HD ") precipitated silica, for example can mention from the silicon-dioxide Ultrasil 7000 of Degussa and Ultrasil 7005, from silicon-dioxide Zeosil 1165MP, the 1135MP of Rhodia and 1115MP, from the silicon-dioxide Hi-Sil EZ150G of PPG, from the silicon-dioxide Zeopol 8715,8745 and 8755 of Huber, and as application WO 03/16837 described silicon-dioxide with high-specific surface area.
When composition of the present invention is intended to when having the tire tread of low-rolling-resistance, used inorganic reinforcing filler, particularly when it is silicon-dioxide, preferably have between 45 and 400 meters squared per gram, more preferably the BET surface-area between 60 and 300 meters squared per gram.
Preferably, reinforcing filler (mixture of carbon black, inorganic reinforcing filler or this two classes filler) total content 20 and 200phr between, more preferably 30 and 150phr between, optimum content depends on specific intended application and difference in known manner: for example, reinforcement level for the expection of bicycle tyre, obviously be lower than for the tire that can under high speed, move with continuous fashion, for example the reinforcement level of the tire of motorcycle tyre, passenger tyre or multi-purpose vehicle (such as heavy vehicle) expection.
According to a preferred specific embodiments of the present invention, use be included in 30 and 150phr between, more preferably 50 and 120phr between mineral filler (particularly silicon-dioxide) and the reinforcing filler of the carbon black chosen wantonly; When having carbon black, preferably with below the 20phr, more preferably 10phr following (for example 0.1 and 10phr between) content use carbon black.
For inorganic reinforcing filler is coupled to diene elastomer, use in known manner at least difunctionality coupling agent (or wedding agent), particularly difunctionality organosilane or organopolysiloxane of the connection of the chemistry be intended between mineral filler (its particle surface) and diene elastomer, to provide enough and/or physical properties.
Especially use multi-sulfur silane (polysulphide silane), it depends on that their ad hoc structure can be " symmetry " or " asymmetric ", for example described in application WO 03/002648 and WO 03/002649.
Specially suitable corresponding to following general formula " symmetry " multi-sulfur silane, as the right and wrong of giving a definition are restrictive:
Z-A-S
n-A-Z, wherein
-n is 2 to 8 integer (being preferably 2 to 5);
-A (is preferably C for the divalent group based on hydrocarbon
1-C
18Alkylidene group or C
6-C
12Arylidene is more particularly C
1-C
10, C especially
1-C
4Alkylidene group, particularly propylidene); And
-Z is corresponding to one of following formula:
Wherein:
-R
1' group is for that replace or unsubstituted, be same to each other or different to each other, and expression C
1-C
18Alkyl, C
5-C
18Cycloalkyl or C
6-C
18Aryl (is preferably C
1-C
6Alkyl, cyclohexyl or phenyl, especially C
1-C
4Alkyl is more particularly methyl and/or ethyl); And
-R
2' group is for that replace or unsubstituted, be same to each other or different to each other, and expression C
1-C
18Alkoxyl group or C
5-C
18Cycloalkyloxy (is preferably and is selected from C
1-C
8Alkoxyl group or C
5-C
8The group of cycloalkyloxy more preferably is selected from C
1-C
4The group of alkoxyl group is in particular methoxyl group and oxyethyl group).
At the mixture corresponding to the polythioalkane TMOS of following formula, in the situation of especially common commercial mixture, the mean value of " n " is preferred mark between 2 and 5, more preferably near 4.But the present invention also can for example (n=2) advantageously carry out with disulphanes TMOS (disulphide alkoxysilane).
As the example of multi-sulfur silane, can mention especially two ((C
1-C
4) alkoxyl group (C
1-C
4) alkyl silyl (C
1-C
4) alkyl) and polysulfide (especially disulphide, trisulphide or tetrasulfide), the polysulfide of two (3-trimethoxy-silylpropyl) or two (3-triethoxysilylpropyltetrasulfide) for example.In these compounds, the special use has formula [(C
2H
5O)
3Si (CH
2)
3S
2]
2Two (3-triethoxysilylpropyltetrasulfide) tetrasulfides of being abbreviated as TESPT, or have formula [(C
2H
5O)
3Si (CH
2)
3S]
2Two (triethoxysilylpropyltetrasulfide) disulphide of being abbreviated as TESPD.As preferred embodiment, also mention two (single (C
1-C
4) alkoxyl group two (C
1-C
4) alkyl silyl propyl group) and polysulfide (especially disulphide, trisulphide or tetrasulfide), be more particularly described two (the monosubstituted ethoxy dimetylsilyl propyl group) tetrasulfides of patent application WO 02/083782.
As the coupling agent except the polythioalkane TMOS, especially mention difunctionality POS (organopolysiloxane) or such as patent application WO 02/30939 and WO 02/31041 described silicol polysulfide (R in following formula
2'=OH), perhaps for example patent application WO2006/125532, WO 2006/125533 and WO 2006/125534 described silane or POS with azo dicarbapentaborane functional group.
In rubber combination of the present invention, the content of coupling agent preferably 4 and 12phr between, more preferably 3 and 8phr between.
But the coupling agent graft polymerization preformer is to diene elastomer or inorganic reinforcing filler.Yet, especially in order to process better the composition under the virgin state, the preferred coupling agent that grafts on the inorganic reinforcing filler or the coupling agent under the free state (i.e. not grafting) of using.
At last, it will be understood by those skilled in the art that and to use have another character reinforcing filler of (especially organic nature) as the filler that is equal to the inorganic reinforcing filler of describing this part, as long as this reinforcing filler is coated with the inorganic layer such as silicon-dioxide, perhaps comprise the functional site that is connected, the especially hydroxyl group sites that to set up with coupling agent between filler and the elastomerics on its surface.
II-3. antioxidant series
Antioxidant series of the present invention has the principal character of two kinds of antioxidants by " A " and " B " expression that comprises combination:
A. corresponding to the N-alkyl-N '-phenyl-p-phenylenediamine of formula (I):
B. corresponding to formula (II) 4,4 ', 4 "-three (alkylamino) triphenylamine:
Wherein, R
1, R
2, R
3And R
4Identical or different, each expression has the linearity of 1 to 12 carbon atom or the alkyl of branching, perhaps has the cycloalkyl of 5 to 8 carbon atoms, and the A/B weight ratio is between 1/10 and 5/1.
Preferably, the A/B weight ratio is between 1/10 and 5/1, more preferably in (namely between 0.14 and 4.0) between 1/7 and 4/1.
Preferably, R
1, R
2, R
3And R
4Identical or different, each expression has the alkyl of 2 to 8 carbon atoms, is preferably selected from ethyl, propyl group (being n-propyl, sec.-propyl), butyl (being normal-butyl, sec-butyl and the tertiary butyl), amyl group, hexyl, heptyl or octyl group; The cycloalkyl (cyclopentyl, cyclohexyl, suberyl or ring octyl group) that perhaps has 5 to 8 carbon atoms, more preferably cyclohexyl.
In such as following formula (I) and compound (II), more preferably use have respectively as shown in the formula (I-bis) and (II-bis), R
1, R
2, R
3And R
4Group be branching compound:
R wherein
5, R
6, R
7, R
8, R
9, R
10, R
11And R
12Be same to each other or different to each other, each expression carbonatoms meets the R that as above provides
1, R
2, R
3And R
4The alkyl of preferred definition.
Compound such as following formula (I-bis) is well known to a person skilled in the art, described in the background technology of presents.
Be known as the antiozonidate of rubber corresponding to as above general formula (II) and compound (II-bis), some in them and their synthesis example are as being described among the patent FR 1,354,536.But do not imagine therein at tire with the application in the diene elastomer composition, say nothing of described tire with intrafascicular application.
R as preferred branching
1, R
2, R
3And R
4The example of group is mentioned the sec.-propyl (a), 1 with following formula especially, 3-dimethylbutyl (b) and Isosorbide-5-Nitrae-dimethyl amyl group (c) group:
Therefore, according to a particularly preferred specific embodiments of the present invention, use one of following two compounds as antioxidant A:
Corresponding to the N-sec.-propyl-N ' of following formula-phenyl-Ursol D (" I-PPD "):
Corresponding to the N-1 of following formula, 3-dimethylbutyl-N '-phenyl-Ursol D (" 6-PPD "):
According to another particularly preferred specific embodiments (its with or not with previous combination), use one of following two compounds as antioxidant B:
Corresponding to following concrete formula 4,4 ', 4 "-three (1,3-dimethylbutyl amino) triphenylamine:
Corresponding to following concrete formula 4,4 ', 4 "-three (Isosorbide-5-Nitrae-3,5-dimethylphenyl amino) triphenylamine:
In rubber combination of the present invention, the content of each antioxidant A and B preferably 0.5 and 5phr between, the content of total antioxidation agent system itself preferably 1 and 10phr between.When pointed minimum value was following, weather resistance turned out to be deficiency; And during the maximum value of surpass recommending, have the risk of the decline of the mechanical property that causes owing to undesirable plasticizing effect.Owing to all these reasons, the content of each antioxidant A and B more preferably 0.5 and 3.0phr between, the content of total antioxidation agent system itself more preferably 1.5 and 4phr between.
II-4. various additives
Rubber combination of the present invention also can comprise for all or some conventional additives of tire (especially tire belt) with rubber combination; extending oil for example; softening agent; except above-mentioned anti-aging protective material those (such as antiozonidate; other chemical antiozonidate or antioxidants); fatigue protective agent; methylene radical; bismaleimides or other strengthen the acceptor of resins and to body; based on sulphur or based on sulphur and/or the superoxide cross-linking system to body; vulcanization accelerator; vulcanization activator or retarding agent; anti-recovery agent (six thiosulfonic acid sodium or N for example; N '-meta-phenylene dual-citraconic imide (N, N '-m-phenylenebiscitraconimide); promote that (for example metal complex or salt (for example contain cobalt to rubber to metal; boron; phosphorus or the lanthanide metal salt as describing among the aforementioned application WO 2005/133666)) bonding system.
Except optional being used for the coupling agent of inorganic reinforcing filler, the isoprene matrix also can contain the reagent that covers these mineral fillers, or can improve in known manner more usually the processing aid of their workability (owing to having improved the dispersion of filler in rubber matrix and the viscosity that has reduced composition).
II-5. rubber combination of the present invention and tire
Especially all or part of rubber matrix that can be used for forming tire (the particularly tire of heavy vehicle or passenger vehicle) band bundle at two ene compositions of front description.
For example they can be used as the rubber (rubber gum) of calendering belt or cord body; no matter described layer is " intersection " layer, protective layer or stirrup layer (at 0 degree); perhaps for example they are intended to form simple rubber pad, band or the bar that does not contain reinforcement; described rubber pad, band or bar radially place top or the bottom of various aforementioned belts; or even insert between the belt; for example to form the sublevel of tyre surface; perhaps place the lateral end of these belts of " shoulder " zone of tire, for example to form decoupling (decoupling) rubber.
For example, single accompanying drawing has schematically shown in the mode of general expression and can meet or not meet the radial section with heavy vehicle tyre 1 of radial carcass reinforcement of the present invention.This tire 1 comprises crown 2, two sidewalls 3, two tyre beads 4, is extended to the radial carcass reinforcement 7 of another tyre bead by a tyre bead.Titled with tyre surface (in order to simplify; demonstration in this synoptic diagram) crown 2 strengthens by the band bundle 6 that is comprised of at least two " intersection " crown layers in known manner; and being coated with at least one crown protective layer, all these layers strengthen by the metal cords (metallic cord) of being made by carbon steel.Two steel bead wires 5 that carcass reinforcement 7 twines in each tyre bead 4, the outside from tire 1 to upper end 8 that for example point to (be shown as here and be contained on its wheel rim 9) of this reinforcement 7.Carcass reinforcement 7 is made with cord body or layer that metal cords strengthens by at least one, described metal cords is called " meridian " cord (" radial " cord), be that in fact these cords are installed in parallel with each other, and from a tyre bead extend to another tyre bead with the center circle side face (plane vertical with the tire rotation axle, it is positioned in the middle of two tyre beads 4, and passes band bundle 6 middle parts) be formed on the angle between 80 ° and 90 °.
Tire of the present invention from above-described embodiment has the principal character that comprises band bundle 6 in its crown 2, and the calendering glue of belt 6 (in this embodiment, two cross-levels and a protective layer) comprises antioxidant series of the present invention.
In the situation of the tire that comprises for example one or more " zero degree " layer, the rubber that preferably is used for the calendering cord, no matter it is the form with form near the layer of the one fixed width of the width of cross-level, narrower bar, or the form of the line that single rubber covers, also based on two ene compositions that comprise antioxidant series of the present invention, especially isoprene composition.
According to a preferred specific embodiments of the present invention, rubber combination based on diene elastomer (especially isoprene elastomerics), reinforcing filler and antioxidant series of the present invention has more than 3 MPas under sulphided state (after namely solidifying), more preferably the elongation secant modulus (MA10) between 5 and 18 MPas.This is within the above-mentioned modulus ranges of the best weather resistance balance of record.
II-6. the preparation of rubber combination
Described rubber combination uses in suitable mixing tank and well known to a person skilled in the art that two continuous production stages make: (be expressed as T at maximum temperature
Max) between 110 ℃ and 190 ℃, the fs (sometimes being called " non-preparation " stage) that preferably the heat engine tool operates or mediates under the high temperature between 130 ℃ and 180 ℃, then be generally below 110 ℃, for example mechanically operated subordinate phase (sometimes being called " preparation " stage) under the lesser temps between 40 ℃ and 100 ℃ adds crosslinked or vulcanization system in this ending phase process.
The manufacture method of composition of the present invention is characterised in that, at least reinforcing filler and antioxidant series of the present invention add by mediating diene elastomer (especially isoprene elastomerics) in the first non-preparatory phase process, namely these various basal component are introduced into mixing tank at least, and the heat engine tool is mediated until reach between 110 ℃ and 190 ℃ in one or more steps, preferably maximum temperature between 130 ℃ and 180 ℃.
For example, the first (non-preparation) stage carried out in single heat engine tool step, in this process in the mixing tank (such as conventional closed mixing tank) that following introducing is suitable: at first, introduce the basal component (diene elastomer, reinforcing filler and antioxidant series) that is necessary, then (for example after mediating 1 to 2 minute) introduces optional supplementary processing auxiliary agent and other the various additives except crosslinked or vulcanization system.Total kneading time of this non-preparatory phase preferably between 2 and 10 minutes.
After cooling gained mixture, usually at low temperatures vulcanization system is added external mixer (such as roll mill); Then the whole mixture of fusion (preparatory phase) several minutes (for example between 5 and 15 minutes).
Then with the calendering of the final composition of gained for the form of the form of for example sheet material (thickness is 2 to 3 millimeters) or rubber film to measure its physics or mechanical property, especially the laboratory characterizes; Perhaps the final composition of gained is extruded the formation rubber profile, described rubber profile for example can be after cutting or being assembled to target sizes, and directly use afterwards adding required fabric or metal reinforcements (such as tire belt).
In a word, the preparation method of the present invention based on the rubber combination of at least a diene elastomer, reinforcing filler, cross-linking system and antioxidant comprises the steps:
Mediate whole mixture until reach maximum temperature between 110 ℃ and 190 ℃ by heat engine tool in one or more stages, add in the diene elastomer (especially isoprene elastomerics) in the mixing tank:
-reinforcing filler; With
-antioxidant series;
Whole mixture is cooled to temperature below 100 ℃;
Then add cross-linking system;
Mediate whole mixture until the maximum temperature below 110 ℃ is characterized in that described antioxidant series comprises at least two kinds of antioxidant A and B in front detailed description of the separately ratio with recommendation.
Sulfuration or solidify and preferably to carry out time enough under the temperature between 130 ℃ and 200 ℃ He under the pressure in known manner, this time depends on solidification value, used vulcanization system especially, vulcanize the size of kinetics and routine as discussed tire and can change between 5 and 90 minutes.
Cross-linking system itself is preferably based on sulphur and main vulcanization accelerator.Various known inferior promotor or vulcanization activators, usually add this vulcanization system such as zinc oxide, stearic acid, guanidine derivative (particularly vulkacit D), vulcanization retarder etc., and in the first non-preparatory phase process and/or in the preparatory phase process, add.Especially when the present invention is applied to heavy vehicle type tire, sulphur with preferably 1 and 10phr between, more preferably 2 and 8phr between content use.Main vulcanization accelerator with preferably 0.5 and 5phr between, more preferably 0.5 and 2phr between content use.
Might use any compound of the vulcanization accelerator that can in the presence of sulphur, serve as diene elastomer as (main or inferior) promotor, especially thiazole type accelerator and derivative, thiuram or zinc dithiocarbamate type promotor.These promotor more preferably are selected from 2-mercaptobenzothiazole disulphide (being abbreviated as MBTS), N cyclohexyl 2 benzothiazole sulfenamide (being abbreviated as CBS), N, the mixture of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (being abbreviated as DCBS), N tert butyl benzothiazole 2 sulfenamide (being abbreviated as TBBS), N tert butyl benzothiazole 2 sulfenamide (being abbreviated as TBSI), zinc dibenzyldithiocarbamate (being abbreviated as ZBEC) or these compounds.Preferably, use sulphenamide type primary accelerator.
Self-evident be the present invention relates to " original " attitude (namely solidify before) in front description and " curing " or sulphided state (namely crosslinked or vulcanize after) rubber combination and tire.
III.
Particular exemplary embodiments
III-1.4,4 ', 4 "-three (1,3-dimethylbutyl is amino) triphenylamines is synthetic
Has the compound of formula (IV-a) according to following synthetic making.
The carbon that 11.0 grams are derived from three (p-aminophenyl) amine of Organica Feinchemie GmbH, 300 milliliters of methyl iso-butyl ketone (MIBK) and 0.8 gram 5% carries platinum and adds in the 0.6 liter of autoclave that is equipped with agitator.When stirring, under the hydrogen pressure that under 160-165 ℃ medium is placed between 2.1 and 3.5 MPas 60 minutes.Then filter this medium to remove catalyzer, then vapourisation under reduced pressure.With the amounts of 20.2 grams obtain 4,4 ', 4 "-three (1,3-dimethylbutyl is amino) triphenylamine resistates is 97.6% purity according to gas-chromatography, and is the form of intense violet color solid.
III-2. the preparation of rubber combination
Following test is carried out as follows: the closed mixing tank is introduced in isoprene elastomerics, reinforcing filler (carbon black), be filled to 70%, the initial room-temperature of this closed mixing tank is about 60 ℃, then after mediating 1 to 2 minute, introduce various other compositions, comprise one or more antioxidants (depending on situation) but do not comprise vulcanization system.Then in 1 or 2 step (the always kneading time equals for example about 7 minutes), carry out the heat engine tool operational phase (non-preparatory phase), until reach about 165-170 ℃ maximum " drippage (dropping) " temperature.Reclaim and cooling gained mixture, then, by mixing all substances (preparatory phase) for example 3 to 10 minutes, vulcanization system (sulphur and sulphenamide primary accelerator) is added 30 ℃ of lower external mixer (equal-finishing rolls (homo-finisher)).
Then with resulting composition or extrude physics or the mechanical property of form to measure them for sheet material (thickness is 2 to 3 millimeters), perhaps roll to prepare the metal cord of the belt (" work " layer) that forms heavy vehicle tyre.
III-3. characterize test
The purpose of this test is explanation, than the first contrast rubber combination that does not use antioxidant with only use second of conventional antioxidant (6-PPD) with formula (III-b) to contrast rubber combination, when tire belt comprised antioxidant series of the present invention, the isoprene composition that is used for tire belt had improved endurance quality.
For this reason, preparation is based on three kinds of compositions of natural rubber:
-the composition (contrast with conventional antioxidant A) that represented by C-1;
-the composition (according to the present invention, have antioxidant A and the B of combination, have identical active constituent content with respect to composition C-1) that represented by C-2
-the composition (according to the present invention, have antioxidant A and the B of combination, have identical active constituent content with respect to composition C-1, but have antioxidant A and the B of different ratios with respect to composition C-2) that represented by C-3
-the composition (according to the present invention, have antioxidant A and the B of combination, have the content of identical conventional antioxidant A with respect to composition C-1) that represented by C-4.
These four kinds of compositions with the identical prescription of trying one's best except character and antioxidant concentration are intended to consist of heavy vehicle tyre with " the calendering glue " of the working lining of band bundle.
Table 1 and 2 provided four kinds of compositions prescription (table 1-is in the content of the various products of phr), the performance of solidifying before and after (lower 60 minutes at 140 ℃) them and with relative unit (r.u.) (initial state and aging after, based on the reference composition C-1 that is set as 100) result of the MFTRA endurance test of meter.
Vulcanization system is comprised of sulphur and sulphenamide.In composition C-3 of the present invention, the antioxidant that the conventional antioxidant of half (6-PPD with formula III-b) is had formula (IV-a) replaces.
Remember compound 6-PPD, be used for the contrast antioxidant that tire (especially tire belt) is used rubber combination, have expanded formula (III-b):
As a comparison, in composition C-2, C-3 and C-4, be used as fill- in 4,4 ', 4 "-three (1,3-dimethylbutyl amino) triphenylamine has formula (IV-a):
It is significantly larger sterically hindered to notice very soon that the second molecule has, and therefore has the diffusibility of reduction, this to those skilled in the art deducibility be unfavorable for effective antifatigue protection.
The result of look-up table 2, at first notice three kinds of composition C-2, C-3 of the present invention and C-4 before solidifying after (rheological property) and the curing (drawing mechanical performance) have the similar rubber performance with reference composition C-1.
For weather resistance (according to the MFTRA fatigue test of paragraph I-D), be necessary that performance and the performance after aging of distinguishing initial state now.
In non-aging (initial state) composition, should notice that the weather resistance of composition C-2 of the present invention, C-3 and C-4 is substantially the same than reference composition C-1.
Therefore, be important to note that before aging composition, replace part (routine) antioxidant A that the weather resistance result is not had any disadvantageous effect with antioxidant B.
Yet, should note only using antioxidant B, in other words, under other identical conditions, replace fully simply antioxidant A to cause the performance that reduces with antioxidant B.
On the other hand, unexpectedly, for composition C-2 of the present invention, C-3 and C-4, observe quite large improved weather resistance (because composition C-2 is 3 times of contrast C-1, composition C-3 is 19 times of contrast, composition C-4 is 13 times of C-1), this improvement only is attributable to replace some antioxidant A with antioxidant B.
Therefore, composition than prior art, Plasticising system of the present invention offers the fatigue resistance of rubber combination general improvements of the present invention, and has the balance between the weather resistance of initial state and the weather resistance after heat aging (its utmost point improves significantly).
This result is so that those skilled in the art expect the high-durability of band bundle of the present invention and tire, particularly for the problem of the separation (" division ") of the crown plies end described in the application's background technology.
Table 1
(1) natural rubber;
(2) carbon black N330 (ASTM level);
(3) N-1,3-dimethylbutyl-N-phenyl-Ursol D (deriving from the SANTOFLEX 6-PPD of Flexsys);
(4) 4,4 ', 4 "-three (1,3-dimethylbutyl is amino) triphenylamine;
(5) zinc oxide (technical grade-Umicore);
(6) Stearin (PRISTERENE 4931-Uniqema); With
(7) N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (from the SANTOCURE DCBS of Flexsys).
Table 2
Claims (21)
1. based on the rubber combination of at least a diene elastomer, reinforcing filler, cross-linking system and antioxidant series, it is characterized in that described antioxidant series comprises at least two kinds of antioxidants " A " and " B ":
A. corresponding to the N-alkyl-N '-phenyl-p-phenylenediamine of formula (I):
B. corresponding to formula (II) 4,4 ', 4 "-three (alkylamino) triphenylamine:
Wherein, R
1, R
2, R
3And R
4Identical or different, each expression has the linearity of 1 to 12 carbon atom or the alkyl of branching, perhaps has the cycloalkyl of 5 to 8 carbon atoms, and the A/B weight ratio is between 1/10 and 5/1.
2. composition according to claim 1, wherein R
1, R
2, R
3And R
4Identical or different, each expression has alkyl or the cyclohexyl of 2 to 8 carbon atoms.
3. composition according to claim 2, wherein R
1, R
2, R
3And R
4Identical or different, each expression is selected from sec.-propyl, 1, the alkyl of 3-dimethylbutyl or Isosorbide-5-Nitrae-dimethyl amyl group.
4. composition according to claim 3, wherein antioxidant A is the N-sec.-propyl-N '-phenyl-Ursol D corresponding to formula (III-a):
5. composition according to claim 3, wherein antioxidant A is the N-1 corresponding to formula (III-b), 3-dimethylbutyl-N '-phenyl-Ursol D:
6. according to claim 3 to 5 each described compositions, wherein antioxidant B be corresponding to formula (IV-a) 4,4 ', 4 "-three (1,3-dimethylbutyl is amino) triphenylamine:
7. according to claim 3 to 5 each described compositions, wherein antioxidant B be corresponding to formula (IV-b) 4,4 ', 4 "-three (Isosorbide-5-Nitrae-dimethyl amyl group is amino) triphenylamine:
8. according to claim 1 to 5 each described compositions, wherein the content of each antioxidant A and B 0.5 and 5phr between.
9. according to claim 1 to 5 each described compositions, wherein the content of each antioxidant A and B 0.5 and 3phr between.
10. according to claim 1 to 5 each described compositions, wherein the A/B weight ratio is between 1/7 and 4/1.
11. according to claim 1 to 5 each described compositions, wherein said diene elastomer is selected from polyhutadiene, natural rubber, synthetic polyisoprenes, butadienecopolymer, isoprene copolymer or these elastomeric adulterants.
12. composition according to claim 11, wherein said diene elastomer are the isoprene elastomerics.
13. composition according to claim 12, wherein said isoprene elastomerics are selected from natural rubber, synthesize suitable-Isosorbide-5-Nitrae-polyisoprene, isoprene copolymer or these elastomeric adulterants.
14. composition according to claim 13, wherein said isoprene elastomerics is natural rubber.
15. one kind according to claim 1 to 14 each described rubber combinations for the manufacture of or the purposes of renovated tyre.
16. the antioxidant series that can be used in particular for the anti-aging protection of rubber composition for tire is characterized in that described system comprises at least two kinds of antioxidants " A " and " B ":
A. corresponding to the N-alkyl-N '-phenyl-p-phenylenediamine of formula (I):
B. corresponding to formula (II) 4,4 ', 4 "-three (alkylamino) triphenylamine:
Wherein, R
1, R
3, R
3And R
4Identical or different, each expression has the linearity of 1 to 12 carbon atom or the alkyl of branching, perhaps has the cycloalkyl of 5 to 8 carbon atoms, and the A/B weight ratio is between 0.1 and 5.0.
17. an antioxidant series according to claim 16 is used for the purposes of the anti-aging protection of rubber combination.
18. a tire, it comprises according to claim 1 to 14 each described rubber combinations.
19. tire according to claim 18, described tire are heavy vehicle tyre.
20. according to claim 18 or 19 described tires, wherein intrafascicular being with of described tire to 14 each described rubber combinations according to claim 1.
21. the preparation method based on the rubber combination of at least a diene elastomer, reinforcing filler, cross-linking system and antioxidant series, described method comprises the steps:
● mediate whole mixture until reach maximum temperature between 110 ℃ and 190 ℃ by heat engine tool in one or more stages, add in the diene elastomer in the mixing tank:
-reinforcing filler; With
-antioxidant series;
● whole mixture is cooled to temperature below 100 ℃;
● then add cross-linking system;
● mediate whole mixture until the maximum temperature below 110 ℃,
And it is characterized in that described antioxidant series comprises at least two kinds of antioxidants " A " and " B ":
A. corresponding to the N-alkyl-N '-phenyl-p-phenylenediamine of formula (I):
B. corresponding to formula (II) 4,4 ', 4 "-three (alkylamino) triphenylamine:
Wherein, R
1, R
2, R
3And R
4Identical or different, each expression has the linearity of 1 to 12 carbon atom or the alkyl of branching, perhaps has the cycloalkyl of 5 to 8 carbon atoms, and the A/B weight ratio is between 0.1 and 5.0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0853145 | 2008-05-15 | ||
| FR0853145A FR2931158B1 (en) | 2008-05-15 | 2008-05-15 | RUBBER COMPOSITION FOR PNEUMATIC INCORPORATING A NEW ANTI-OXIDANT SYSTEM |
| PCT/EP2009/055842 WO2009138460A1 (en) | 2008-05-15 | 2009-05-14 | Rubber composition for tyre including a novel anti-oxidant system |
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| CN102027055A CN102027055A (en) | 2011-04-20 |
| CN102027055B true CN102027055B (en) | 2013-01-23 |
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|---|---|
| US (2) | US8833417B2 (en) |
| EP (1) | EP2285886B1 (en) |
| JP (1) | JP5498485B2 (en) |
| CN (1) | CN102027055B (en) |
| AT (1) | ATE541887T1 (en) |
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| FR2991916B1 (en) * | 2012-06-18 | 2014-07-11 | Michelin & Cie | TIRE FOR HIGH-LOAD VEHICLE |
| US10160718B2 (en) | 2015-12-22 | 2018-12-25 | Eastman Chemical Company | Methods of making compounds having antidegradant and antifatigue efficacy |
| US10167252B2 (en) | 2015-12-22 | 2019-01-01 | Eastman Chemical Company | Compounds and mixtures with antidegradant and antifatigue efficacy and compositions including such compounds |
| US10287418B2 (en) | 2015-12-22 | 2019-05-14 | Eastman Chemical Company | Compounds with antidegradant and antifatigue efficacy and compositions including said compounds |
| US10260017B2 (en) | 2015-12-22 | 2019-04-16 | Eastman Chemical Company | Compounds and mixtures with antidegradant and antifatigue efficacy and compositions including said compounds |
| US10428009B2 (en) | 2015-12-22 | 2019-10-01 | Eastman Chemical Company | Methods of making compounds and mixtures having antidegradant and antifatigue efficacy |
| JP6485374B2 (en) * | 2016-01-21 | 2019-03-20 | 株式会社村田製作所 | Coil parts |
| FR3060570A1 (en) | 2016-12-19 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | PROCESS FOR THE PREPARATION OF A DIODE MODEL ELASTOMER MODIFIED BY A 1,3-DIPOLAR COMPOUND BY REACTIVE EXTRUSION |
| FR3060571A1 (en) | 2016-12-19 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | PROCESS FOR PREPARING A DIODE MODIFIED ELASTOMER WITH 1,3-DIPOLAR COMPOUND |
| FR3060582A1 (en) | 2016-12-21 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | PROCESS FOR THE PREPARATION OF POLYDIENE / POLYLACTIDE COPOLYMERS BY REACTIVE EXTRUSION |
| FR3060454A1 (en) | 2016-12-21 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | RUBBER COMPOSITION COMPRISING A POLYDIENE / POLYLACTIDE COPOLYMER |
| WO2018226372A1 (en) | 2017-06-09 | 2018-12-13 | Eastman Chemical Company | Methods of making compounds having antidegradant and antifatigue efficacy |
| CN110691769B (en) | 2017-06-09 | 2023-03-10 | 伊士曼化工公司 | Compounds and mixtures having antidegradants and antifatigue efficacy and compositions comprising said compounds |
| EP3634940B1 (en) | 2017-06-09 | 2021-07-14 | Eastman Chemical Company | Compounds and mixtures with antidegradant and antifatigue efficacy and compositions including such compounds |
| WO2018226375A1 (en) | 2017-06-09 | 2018-12-13 | Eastman Chemical Company | Methods of making compounds and mixtures having an antidegradant and antifatigue efficacy |
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| DE102020211872A1 (en) | 2020-09-23 | 2022-03-24 | Continental Reifen Deutschland Gmbh | Process for obtaining natural rubber, rubber composition with natural rubber and use thereof |
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| FR2900156B1 (en) * | 2006-04-20 | 2008-07-04 | Michelin Soc Tech | PNEUMATIC BELT INCORPORATING AN ANTIOXIDANT AGENT. |
| EP2048192B1 (en) * | 2006-10-05 | 2011-04-20 | Sumitomo Rubber Industries, Ltd. | Rubber composition for clinch apex and pneumatic tire with clinch apex utilizing the same |
-
2008
- 2008-05-15 FR FR0853145A patent/FR2931158B1/en not_active Expired - Fee Related
-
2009
- 2009-05-14 CN CN2009801168242A patent/CN102027055B/en not_active Expired - Fee Related
- 2009-05-14 WO PCT/EP2009/055842 patent/WO2009138460A1/en active Application Filing
- 2009-05-14 JP JP2011508922A patent/JP5498485B2/en not_active Expired - Fee Related
- 2009-05-14 US US12/992,830 patent/US8833417B2/en not_active Expired - Fee Related
- 2009-05-14 EP EP09745792A patent/EP2285886B1/en not_active Not-in-force
- 2009-05-14 AT AT09745792T patent/ATE541887T1/en active
-
2014
- 2014-08-26 US US14/468,947 patent/US20150031810A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1589293A (en) * | 2001-11-26 | 2005-03-02 | 米其林技术公司 | Rubber composition for tread and method for manufacturing same |
| WO2004033548A1 (en) * | 2002-10-11 | 2004-04-22 | Societe De Technologie Michelin | Tyre belt based on an inorganic filler and a polysulphide silane |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110303338A1 (en) | 2011-12-15 |
| FR2931158A1 (en) | 2009-11-20 |
| US20150031810A1 (en) | 2015-01-29 |
| JP2011521041A (en) | 2011-07-21 |
| EP2285886B1 (en) | 2012-01-18 |
| US8833417B2 (en) | 2014-09-16 |
| EP2285886A1 (en) | 2011-02-23 |
| FR2931158B1 (en) | 2010-07-30 |
| CN102027055A (en) | 2011-04-20 |
| WO2009138460A1 (en) | 2009-11-19 |
| JP5498485B2 (en) | 2014-05-21 |
| ATE541887T1 (en) | 2012-02-15 |
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